JPH026759B2 - - Google Patents
Info
- Publication number
- JPH026759B2 JPH026759B2 JP55145840A JP14584080A JPH026759B2 JP H026759 B2 JPH026759 B2 JP H026759B2 JP 55145840 A JP55145840 A JP 55145840A JP 14584080 A JP14584080 A JP 14584080A JP H026759 B2 JPH026759 B2 JP H026759B2
- Authority
- JP
- Japan
- Prior art keywords
- cobalt
- acetylacetonate
- acetylacetone
- hydrogen peroxide
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 40
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002904 solvent Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims description 51
- 229910017052 cobalt Inorganic materials 0.000 claims description 51
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 51
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 230000002745 absorbent Effects 0.000 claims 1
- 239000002250 absorbent Substances 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 2
- FCEOGYWNOSBEPV-FDGPNNRMSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FCEOGYWNOSBEPV-FDGPNNRMSA-N 0.000 abstract 2
- JUPWRUDTZGBNEX-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O JUPWRUDTZGBNEX-UHFFFAOYSA-N 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 5
- 229910001628 calcium chloride Inorganic materials 0.000 description 5
- 239000001110 calcium chloride Substances 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001868 cobalt Chemical class 0.000 description 3
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000004809 thin layer chromatography Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/77—Preparation of chelates of aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/92—Ketonic chelates
Abstract
Description
【発明の詳細な説明】
本発明は、コバルト()−アセチルアセトネ
ートを過酸化水素とアセチルアセトンの存在で反
応させることによりコバルト()−アセチルア
セトネートを製造する方法に関する。反応は、特
別の方法で製造され、溶解された出発物質を用い
て行なわれる。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing cobalt()-acetylacetonate by reacting cobalt()-acetylacetonate in the presence of hydrogen peroxide and acetylacetone. The reaction is carried out using starting materials prepared in a special manner and dissolved.
コバルト()−アセチルアセトネートを過酸
化水素及びアセチルアセトンと反応させてコバル
ト()−アセチルアセトネートにすることは、
ドイツ連邦共和国特許出願公告第2420691号公報
(NOA7503276)から公知である。この場合には、
コバルト()−塩を水溶液中でアセチルアセト
ンと公知方法により反応させて製造されたコバル
ト()−アセチルアセトネートから出発する。
この方法で製造したコバルト()−アセチルア
セトネートは常に2モルの結晶水を含み、この結
晶水は極めて不経済な方法でしか除去できない。 Reacting cobalt()-acetylacetonate with hydrogen peroxide and acetylacetone to form cobalt()-acetylacetonate is
It is known from German Patent Application No. 2420691 (NOA7503276). In this case,
The starting point is cobalt()-acetylacetonate, which is prepared by reacting a cobalt()-salt with acetylacetone in aqueous solution by known methods.
The cobalt()-acetylacetonate prepared in this way always contains 2 mol of water of crystallization, which can only be removed in a very uneconomical manner.
更に、この公知方法では任意の有機溶剤中で酸
化を実施し、その際有利な溶剤は芳香族炭化水素
又はアルコールである。この方法では、その製造
自体が既に極めて不経済な、予め調製したコバル
ト()−アセチルアセトネートから出発しなけ
ればならないという欠点がある。即ち、この公知
製造方法では反応生成物をアンモニアで中和させ
なければならず、引続きアンモニウム塩を注意深
く洗浄しなければならない。 Furthermore, the known process carries out the oxidation in any organic solvent, preferred solvents being aromatic hydrocarbons or alcohols. This process has the disadvantage that it has to start from pre-prepared cobalt()-acetylacetonate, the production of which is already extremely uneconomical. In this known process, the reaction product must therefore be neutralized with ammonia and the ammonium salt must then be carefully washed off.
ドイツ連邦共和国特許出願公告第2420691号公
報では、純粋なコバルト()−アセチルアセト
ネートを使用するにもかかわらず、無水のコバル
ト()−アセチルアセトネートの75〜85%の収
率しか得られない。 In German Patent Application No. 2420691, despite using pure cobalt()-acetylacetonate, only 75-85% yields of anhydrous cobalt()-acetylacetonate are obtained. .
従つて、コバルト()−アセチルアセトネー
トを、出来るだけ95%以上の収率を得るように製
造するという課題がある。更に、単離したコバル
ト()−アセチルアセトネートから出発しなく
てよいコバルト()−アセチルアセトネートの
製法を見い出すという課題があつた。 Therefore, there is a problem of producing cobalt ()-acetylacetonate in a yield as high as 95% or higher. A further problem was to find a process for producing cobalt ()-acetylacetonate that does not require starting from isolated cobalt ()-acetylacetonate.
この課題を解決するに当つて、120℃までの温
度で過酸化水素に対して不活性の有機溶剤とし
て、コバルト()−アセチルアセトネートが製
造されるアセトン、ジオキサン、ジオキソラン又
はテトラヒドロフランの群から選択されるケトン
を使用することを特徴とする、有機溶剤中でアセ
チルアセトンの存在で過酸化水素を用いてコバル
ト()−アセチルアセトネートを酸化すること
によつてコバルト()−アセチルアセトネート
を製造する方法を見い出した。 In solving this task, cobalt()-acetylacetonate is prepared as an organic solvent inert towards hydrogen peroxide at temperatures up to 120 °C, selected from the group of acetone, dioxane, dioxolane or tetrahydrofuran. cobalt()-acetylacetonate by oxidation of cobalt()-acetylacetonate with hydrogen peroxide in the presence of acetylacetone in an organic solvent, characterized in that a ketone is used. I found a way.
この本発明方法を適用する場合には、コバルト
()−化合物から直接コバルト()−アセチル
アセトネートを得ることができ、中間生成物を単
離しなくてよく、不経済な中間精製工程を実施し
なくてよい。この場合コバルト()−化合物に
対して95%以上の収率が得られる。得られる生成
物はほぼ無水であり、コバルト()塩を含まな
い。 When applying the method of the present invention, cobalt()-acetylacetonate can be obtained directly from cobalt()-compounds, there is no need to isolate intermediate products, and an uneconomical intermediate purification step is not performed. You don't have to. In this case, a yield of 95% or more can be obtained based on the cobalt()-compound. The resulting product is nearly anhydrous and free of cobalt() salts.
相応する溶剤の選択は本発明方法において重要
である。ドイツ連邦共和国特許出願公告第
2420691号公報に挙げられている溶剤は本発明方
法の実施には適当でなく、水と混和しないか、又
は高温で過酸化水素に対して不活性ではない。 The selection of a suitable solvent is important in the process according to the invention. Federal Republic of Germany Patent Application Publication No.
The solvents mentioned in publication No. 2,420,691 are not suitable for carrying out the process of the invention and are not miscible with water or inert towards hydrogen peroxide at elevated temperatures.
本発明により使用しうる有利な溶剤はアセトン
である。 A preferred solvent that can be used according to the invention is acetone.
本発明方法は、更に、コバルト()−アセチ
ルアセトンから出発し、これを未単離の形で使用
することを特徴とする。この手段は、コバルト
()−アセチルアセトネートの製造を特許請求の
範囲に記載した溶剤中で実施することによつて達
成される。製造自体はコバルト()−化合物を
アセチルアセトンと高温で反応させることによつ
て自体公知の方法で行なう。この場合、コバルト
化合物としてCo(OH)2、CoO又は塩基性炭酸コ
バルトを使用する。反応温度は20〜100℃である。
溶剤の沸騰温度で操作するのが有利である。蒸発
した溶剤を、同時に蒸発した水を捕捉する吸水剤
を介して凝縮液を流す方法で凝縮させるように実
施することもできる。残りの凝縮液は再び反応容
器中に導びく、この方法で反応進行を調節し、コ
バルト()−アセチルアセトネートを形成する
反応の終点を知ることができる。 The process according to the invention is further characterized in that it starts from cobalt()-acetylacetone and uses it in unisolated form. This measure is achieved by carrying out the preparation of cobalt()-acetylacetonate in the claimed solvent. The production itself is carried out in a manner known per se by reacting a cobalt() compound with acetylacetone at high temperatures. In this case, Co(OH) 2 , CoO or basic cobalt carbonate is used as the cobalt compound. The reaction temperature is 20-100°C.
It is advantageous to operate at the boiling temperature of the solvent. It is also possible to condense the evaporated solvent by flowing the condensate through a water-absorbing agent that simultaneously captures the evaporated water. The remaining condensate is again introduced into the reaction vessel, and in this way the reaction progress can be controlled and the end point of the reaction forming cobalt()-acetylacetonate can be known.
コバルト()−化合物と共に反応混合物に添
加するアセチルアセトンの量は、少なくともコバ
ルト()−アセチルアセトネートを製造するた
め化学量論的に必要な量である。しかしまた全反
応の初めに、所望のコバルト()−アセチルア
セトンを生成するため化学量論的に必要な量のア
セチルアセトンを装入することもできる。 The amount of acetylacetone added to the reaction mixture together with the cobalt()-compound is at least the amount stoichiometrically necessary to produce cobalt()-acetylacetonate. However, it is also possible to introduce at the beginning of the entire reaction the stoichiometrically necessary amount of acetylacetone to form the desired cobalt()-acetylacetone.
本発明による溶剤中での操作法では、結合水を
含まないコバルト()−アセチルアセトネート
が中間に生成する。この化合物は本発明による溶
剤中に溶解しており、単離することなく、この溶
液中で常法でH2O2で酸化してコバルト()−ア
セチルアセトネートとする。酸化を、化学量論的
に必要な量のアセチルアセトンの存在で実施す
る。 In the method of operation according to the invention in a solvent, a cobalt()-acetylacetonate which is free of bound water is formed as an intermediate. This compound is dissolved in the solvent according to the invention and, without being isolated, is oxidized in this solution with H 2 O 2 in the customary manner to give cobalt()-acetylacetonate. The oxidation is carried out in the presence of the required stoichiometric amount of acetylacetone.
この反応の際には40〜100℃、好ましくは50〜
90℃の温度範囲で操作する。溶剤の沸騰温度で操
作するのが有利である。 During this reaction, 40-100℃, preferably 50-100℃
Operate in a temperature range of 90°C. It is advantageous to operate at the boiling temperature of the solvent.
過酸化水素は25〜35%水溶液として添加するの
が好ましい。完全な酸化を達成するためには、10
重量%までの小過剰で既に充分である。一般に、
1.1〜1.5モル過剰を使用する。 Hydrogen peroxide is preferably added as a 25-35% aqueous solution. To achieve complete oxidation, 10
A small excess of up to % by weight is already sufficient. in general,
A 1.1-1.5 molar excess is used.
過酸化水素を少量ずつ添加し、常に添加直後に
反応しうるようにするのが有利である。コバルト
()塩がもはや存在しない場合に、過酸化水素
の添加を終了する。これは試料の薄層クロマトグ
ラフイーによつて容易に証明することができる。 It is advantageous to add the hydrogen peroxide in small portions so that it is always ready to react immediately after addition. The addition of hydrogen peroxide is terminated when no more cobalt () salt is present. This can be easily verified by thin layer chromatography of samples.
全部のコバルト()−塩がコバルト()−塩
に酸化されたら、25〜10℃の温度に冷却する。そ
の際コバルト()−アセチルアセトネートが無
水塩として生じる。これは90℃までの温度で容易
に乾燥することができる。乾燥は真空中での操作
によつて容易にされ、その際30ミリバール以上の
真空で完全に充分である。 Once all the cobalt()-salts have been oxidized to cobalt()-salts, cool to a temperature of 25-10°C. Cobalt()-acetylacetonate is thereby formed as an anhydrous salt. It can be easily dried at temperatures up to 90°C. Drying is facilitated by operation in a vacuum, a vacuum of 30 mbar or more being completely sufficient.
コバルト()−アセチルアセトネートの結晶
を分離した後、バツチの母液を新しいバツチに心
配なく装入することができる。反応の際に障害と
なりうる副生成物は言うに足る程生じない。 After separation of the cobalt()-acetylacetonate crystals, the mother liquor of the batch can be charged to a new batch without worry. Not a significant amount of by-products, which could be a hindrance during the reaction, are produced.
例 1
還流冷却器及び蒸留ブリツジを設けた反応容器
中で水酸化コバルト93gをアセトン300ml中に懸
濁する。撹拌下にアセチルアセトン315gを添加
する。その際緩和な加温が起る。Example 1 93 g of cobalt hydroxide are suspended in 300 ml of acetone in a reaction vessel equipped with a reflux condenser and a distillation bridge. Add 315 g of acetylacetone while stirring. At this time, mild heating occurs.
混合物を加熱還流し、留出するアセトンを塩化
カルシウム上に導通し、同伴した水を吸収させ
る。沸騰温度に2時間加熱した後、塩化カルシウ
ムは著量の水を結合していた。 The mixture is heated to reflux and the acetone distilled out is passed over calcium chloride to absorb the entrained water. After heating to boiling temperature for 2 hours, the calcium chloride had bound a significant amount of water.
その後3〜3 1/2時間の間に過酸化水素100g
を35%水溶液として滴下ロートから添加した。こ
の場合反応混合物を還流下に保持した。蒸留ブリ
ツジを除去した。内温は60〜65℃であつた。 100g of hydrogen peroxide over the next 3 to 3 1/2 hours
was added from the dropping funnel as a 35% aqueous solution. In this case the reaction mixture was kept under reflux. The distillation bridge was removed. The internal temperature was 60-65°C.
合計100gの過酸化水素溶液を添加した後、試
料から薄層クロマトグラフイーを取つた。コバル
ト()−塩がもはや存在しなかつたことが判つ
た。次に反応混合物を10℃に冷却した。沈殿する
緑/黒色の結晶を濾取し、アセトン75mlで洗浄し
た。生成物を空気中で最高0.2%の含水率まで乾
燥することができた。この方法でコバルト()
−アセチルアセトネート338.7gが得られた(収
率=使用した水酸化コバルトに対して95.1%)。
分析によれば金属含有率は16.54〜16.59%であつ
た。理論値は16.57%である。 After adding a total of 100 g of hydrogen peroxide solution, the sample was subjected to thin layer chromatography. It was found that the cobalt()-salt was no longer present. The reaction mixture was then cooled to 10°C. The precipitated green/black crystals were collected by filtration and washed with 75 ml of acetone. The product could be dried in air to a moisture content of up to 0.2%. In this way cobalt()
338.7 g of acetylacetonate were obtained (yield=95.1% based on the cobalt hydroxide used).
According to analysis, the metal content was 16.54-16.59%. The theoretical value is 16.57%.
例 2
例1の母液及び洗浄水中に水酸化コバルト93g
を懸濁し、引続きアセチルアセトン315gを添加
する。混合物を撹拌しながら還流温度にし、その
際留出したアセトンを例1と同様に塩化カルシウ
ム上で乾燥した。Example 2 93g of cobalt hydroxide in the mother liquor and wash water of Example 1
and then 315 g of acetylacetone are added. The mixture was brought to reflux temperature with stirring, and the acetone distilled off was dried as in Example 1 over calcium chloride.
2時間の反応時間後、35%過酸化水素溶液の滴
加を始めた。その際内温は60〜65℃に上昇した。
3時間の間に合計95gの過酸化水素を添加した。 After a reaction time of 2 hours, the dropwise addition of 35% hydrogen peroxide solution was started. At that time, the internal temperature rose to 60-65°C.
A total of 95 g of hydrogen peroxide was added over the course of 3 hours.
この時間の経過後、試料を薄層クロマトグラフ
イーによりコバルト()−塩がもはや存在しな
いことが判つた。その後更に10℃に冷却したとこ
ろ、大きい黒色結果が沈殿した。これを濾別し、
アセトン80mlで洗浄した。 After this time had elapsed, the sample was subjected to thin layer chromatography to show that no cobalt()-salt was present any longer. Upon further cooling to 10° C., large black particles precipitated. Filter this and
Washed with 80 ml of acetone.
洗浄した結晶を引続き40ミリバールの真空で80
℃で1時間乾燥した。コバルト()−アセチル
アセトネート344g(収率96.6%)が得られた。
金属含有率は16.48〜16.56%であり、含水率は最
高0.1%であつた。 The cleaned crystals are then vacuumed at 40 mbar for 80
It was dried at ℃ for 1 hour. 344 g (yield 96.6%) of cobalt ()-acetylacetonate was obtained.
The metal content was 16.48-16.56% and the water content was up to 0.1%.
例 3
この例は、生ずる水を吸収しなくてもコバルト
()−アセチルアセトネートを製造しうることを
示す。Example 3 This example shows that cobalt ()-acetylacetonate can be prepared without absorbing the resulting water.
アセトン300ml中に塩基性炭酸コバルト128gを
懸濁した。更に室温でアセチルアセトン210gを
添加した。この際既に反応が起り、この反応はガ
ス発生及び変色によつて知ることができる。混合
物を還流温度に加熱し、その後アセチルアセトン
105gを添加し、更に1時間還流下に保持する。 128 g of basic cobalt carbonate was suspended in 300 ml of acetone. Furthermore, 210 g of acetylacetone was added at room temperature. A reaction already takes place, which can be detected by the evolution of gas and a change in color. Heat the mixture to reflux temperature and then add acetylacetone
Add 105 g and keep under reflux for a further hour.
引続き、滴下ロートより35%過酸化水素溶液の
滴加を始める。この方法で4 1/2時間以内に過酸
化水素100gを添加する。この時間の経過後、薄
層クロマトグラムによりコバルト()塩がもは
や存在しないことが判つた。 Next, start adding 35% hydrogen peroxide solution dropwise from the dropping funnel. In this manner, 100 g of hydrogen peroxide is added within 4 1/2 hours. After this time, a thin layer chromatogram showed that cobalt() salt was no longer present.
反応混合物を10℃に冷却した後、この際得られ
た結晶を濾取し、アセトン75mlで洗浄した。得ら
れた固体を40ミリバールの真空で80℃で1時間乾
燥した。生成物343g(理論量の95.4%)が得ら
れた。分析により16.51〜16.58%の金属含有率が
生じた。含水率は最高0.2%であつた。 After cooling the reaction mixture to 10° C., the crystals obtained at this time were collected by filtration and washed with 75 ml of acetone. The solid obtained was dried at 80° C. for 1 hour in a vacuum of 40 mbar. 343 g (95.4% of theory) of product were obtained. Analysis yielded a metal content of 16.51-16.58%. The maximum moisture content was 0.2%.
例 4
例3の母液及び洗浄水に、塩化カルシウム上で
乾燥した後、アセトン90mlを添加する。この溶液
中に塩基性炭酸コバルト128gを懸濁する。引続
き撹拌下にアセチルアセトン215gを添加する。
直ちに、変色及び結晶形で反応を認めることがで
きる。更にガス発生が起り、混合物は明らかに撹
拌性が悪くなる。Example 4 To the mother liquor and wash water of Example 3, after drying over calcium chloride, 90 ml of acetone are added. 128 g of basic cobalt carbonate are suspended in this solution. 215 g of acetylacetone are subsequently added while stirring.
The reaction can be observed immediately with a color change and crystalline form. Furthermore, gas evolution occurs and the mixture becomes noticeably less stirrable.
その後、混合物を還流温度に加熱し、更にアセ
チルアセトン105gを添加する。更に約半時間煮
沸還流し、留出するアセトンを塩化カルシウム上
に導びく。引続き、35%過酸化水素溶液の滴加を
始める。 The mixture is then heated to reflux temperature and a further 105 g of acetylacetone are added. The mixture is further boiled and refluxed for about half an hour, and the acetone distilled out is introduced onto calcium chloride. Next, start adding the 35% hydrogen peroxide solution dropwise.
4 1/2時間経過後、過酸化水素92gを添加し、
コバルト()塩についての試験は陰性になつ
た。その後、反応混合物を10℃に冷却した。その
際緑色/黒色の結晶が得られ、これを濾過し、ア
セトン75mlで洗浄した。結晶を引続き室温で乾燥
した。 After 4 1/2 hours, add 92g of hydrogen peroxide,
Tests for cobalt() salts came back negative. The reaction mixture was then cooled to 10°C. Green/black crystals were obtained, which were filtered and washed with 75 ml of acetone. The crystals were subsequently dried at room temperature.
コバルト()−アセチルアセトネート346g
(理論量の97.2%)が得られた。分析すると、
16.55〜16.56%のコバルト含有率を生じた。含水
率は0.2%以下であつた。 Cobalt ()-acetylacetonate 346g
(97.2% of the theoretical amount) was obtained. When analyzed,
Resulting in a cobalt content of 16.55-16.56%. The moisture content was 0.2% or less.
例 5
塩基性炭酸コバルト128gをアセトン40ml中で
撹拌した。混合物を撹拌下に還流させると、その
際内温は66℃であつた。アセチルアセトン315g
を添加した。その後4時間の間に過酸化水素(35
%溶液)を滴加した。この時間の経過後に過酸化
水素の合計量は100gであつた。引続き更に半時
間反応させた。その後、反応混合物を15℃に冷却
し、得られた結晶を濾取し、アセトン100mlで洗
浄した。次に45ミリバールの真空で90℃で乾燥し
た。Example 5 128 g of basic cobalt carbonate was stirred in 40 ml of acetone. The mixture was brought to reflux with stirring, the internal temperature being 66°C. Acetylacetone 315g
was added. During the next 4 hours, hydrogen peroxide (35
% solution) was added dropwise. After this time the total amount of hydrogen peroxide was 100g. The reaction was continued for another half hour. Thereafter, the reaction mixture was cooled to 15° C., and the resulting crystals were collected by filtration and washed with 100 ml of acetone. It was then dried at 90°C under a vacuum of 45 mbar.
含水率最高0.2%及び金属含有率16.54〜16.59%
のコバルト()−アセチルアセトネート336g
(94.4%)が得られた。 Moisture content max. 0.2% and metal content 16.54~16.59%
Cobalt()-acetylacetonate 336g
(94.4%) was obtained.
残留する母液から含水率11.8%のアセトン410
mlを留出させた。この母液を蒸発する際に再びコ
バルト()−アセチルアセトネートが沈殿した。
これを濾過し、前記のように乾燥した。この方法
で再びコバルト()−アセチルアセトネート11
gが得られ、総収量は347g(=使用した炭酸コ
バルトに対して97.5%)であつた。 Acetone 410 with a moisture content of 11.8% from the remaining mother liquor
ml was distilled off. Upon evaporation of this mother liquor, cobalt()-acetylacetonate was again precipitated.
This was filtered and dried as before. In this way again cobalt()-acetylacetonate 11
g, with a total yield of 347 g (=97.5% based on the cobalt carbonate used).
Claims (1)
ルアセトンの存在で過酸化水素を用いてコバルト
()−アセチルアセトネートを酸化することによ
つてコバルト()−アセチルアセトネートを製
造するため、過酸化水素に対して不活性の有機溶
剤として、コバルト()−アセチルアセトネー
トが製造されるアセトン、ジオキサン、ジオキソ
ラン又はテトラヒドロフランの群から選択される
ケトンを使用することを特徴とするコバルト
()−アセチルアセトネートの製法。 2 溶剤としてアセトンを使用する特許請求の範
囲第1項記載の製法。 3 コバルト()−アセチルアセトネートを製
造する際に、コバルト()−アセチルアセトネ
ートの製造に必要な過剰量のアセチルアセトンを
用いて操作する特許請求の範囲第1項又は第2項
記載の製法。 4 コバルト()−化合物とアセチルアセトン
との反応を溶剤の沸騰温度で還流下に実施する特
許請求の範囲第1項から第3項までのいずれか1
項記載の製法。 5 還流する溶剤を水用吸収剤を介して導びく特
許請求の範囲第4項記載の製法。[Claims] 1. Cobalt()-acetylacetonate by oxidizing cobalt()-acetylacetonate with hydrogen peroxide in the presence of the stoichiometrically required amount of acetylacetone in an organic solvent. cobalt()-acetylacetonate is prepared by using, as an organic solvent inert towards hydrogen peroxide, a ketone selected from the group of acetone, dioxane, dioxolane or tetrahydrofuran, from which cobalt()-acetylacetonate is prepared. A method for producing cobalt ()-acetylacetonate. 2. The manufacturing method according to claim 1, which uses acetone as a solvent. 3. The production method according to claim 1 or 2, wherein cobalt ()-acetylacetonate is produced using an excess amount of acetylacetone necessary for producing cobalt ()-acetylacetonate. 4. Any one of claims 1 to 3, wherein the reaction between the cobalt ()-compound and acetylacetone is carried out under reflux at the boiling temperature of the solvent.
Manufacturing method described in section. 5. The manufacturing method according to claim 4, wherein the refluxing solvent is introduced through a water absorbent.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL7907742A NL7907742A (en) | 1979-10-19 | 1979-10-19 | PROCESS FOR PREPARING COBALT (III) ACETYL ACETONATE. |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5677293A JPS5677293A (en) | 1981-06-25 |
JPH026759B2 true JPH026759B2 (en) | 1990-02-13 |
Family
ID=19834050
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP14584080A Granted JPS5677293A (en) | 1979-10-19 | 1980-10-20 | Manufacture of cobalt*iii**acetylacetonate |
Country Status (7)
Country | Link |
---|---|
US (1) | US4338254A (en) |
EP (1) | EP0028308B1 (en) |
JP (1) | JPS5677293A (en) |
AT (1) | ATE3276T1 (en) |
CA (1) | CA1143743A (en) |
DE (1) | DE3063159D1 (en) |
NL (1) | NL7907742A (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4231622C2 (en) * | 1992-09-22 | 1996-09-05 | Bakelite Ag | Process for the production of metal neutral complexes with a high coordination number and their use |
KR100553633B1 (en) * | 1997-03-07 | 2006-02-22 | 타고르 게엠베하 | Preparation of Preparing Substituted Indanones |
AU2002368493A1 (en) * | 2002-12-23 | 2004-07-14 | Council Of Scientific And Industrial Research | Process for the preparation of metal acetylacetonates |
WO2004056737A1 (en) | 2002-12-23 | 2004-07-08 | Council Of Scientific And Industrial Research | Process for the preparation of metal acetylacetonates |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS50149629A (en) * | 1974-04-29 | 1975-11-29 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL137589C (en) * | 1967-09-21 |
-
1979
- 1979-10-19 NL NL7907742A patent/NL7907742A/en not_active Application Discontinuation
-
1980
- 1980-09-20 AT AT80105657T patent/ATE3276T1/en not_active IP Right Cessation
- 1980-09-20 DE DE8080105657T patent/DE3063159D1/en not_active Expired
- 1980-09-20 EP EP80105657A patent/EP0028308B1/en not_active Expired
- 1980-10-16 US US06/197,462 patent/US4338254A/en not_active Expired - Lifetime
- 1980-10-17 CA CA000362632A patent/CA1143743A/en not_active Expired
- 1980-10-20 JP JP14584080A patent/JPS5677293A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS50149629A (en) * | 1974-04-29 | 1975-11-29 |
Also Published As
Publication number | Publication date |
---|---|
EP0028308B1 (en) | 1983-05-11 |
EP0028308A1 (en) | 1981-05-13 |
NL7907742A (en) | 1981-04-22 |
CA1143743A (en) | 1983-03-29 |
US4338254A (en) | 1982-07-06 |
DE3063159D1 (en) | 1983-06-16 |
JPS5677293A (en) | 1981-06-25 |
ATE3276T1 (en) | 1983-05-15 |
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